Fabric print medium

ABSTRACT

A fabric print medium comprising a fabric base substrate; a primary coating composition with a polymeric binder and filler particles applied to, at least, one side of the fabric base substrate; an image-receiving coating composition with a first and a second crosslinked polymeric network applied over the primary coating composition; and a barrier layer comprising a water-repellent agent and a physical gelling compound. Also disclosed are the method for making such fabric print medium and the method for producing printed images using said material.

BACKGROUND

Inkjet printing technology has expanded its application to large formathigh-speed, commercial and industrial printing, in addition to home andoffice usage, because of its ability to produce economical, highquality, multi-colored prints. This technology is a non-impact printingmethod in which an electronic signal controls and directs droplets or astream of ink that can be deposited on a wide variety of mediumsubstrates. Inkjet printing technology has found various applications ondifferent substrates including, for examples, cellulose paper, metal,plastic, fabric and the like. The substrate plays a key role in theoverall image quality and permanence of the printed images.

Textile printing has various applications including the creation ofsigns, banners, artwork, apparel, wall coverings, window coverings,upholstery, pillows, blankets, flags, tote bags, etc. It is a growingand evolving area and is becoming a trend in the visual communicationmarket. As the area of textile printing continues to grow and evolve,the demand for new print mediums increases.

BRIEF DESCRIPTION OF THE DRAWING

The drawings illustrate various examples of the present print medium andare part of the specification.

FIG. 1 is a cross-sectional view of the fabric print medium according toone example of the present disclosure.

FIG. 2 is a flowchart illustrating a method for producing the fabricprint medium according to some examples of the present disclosure.

FIG. 3 is a flowchart illustrating a method for producing printed imagesaccording to some examples of the present disclosure.

DETAILED DESCRIPTION

Before particular examples of the present disclosure are disclosed anddescribed, it is to be understood that the present disclosure is notlimited to the particular process and materials disclosed herein. It isalso to be understood that the terminology used herein is used fordescribing particular examples only and is not intended to be limiting,as the scope of protection will be defined by the claims and equivalentsthereof. In describing and claiming the present article and method, thefollowing terminology will be used: the singular forms “a”, “an”, and“the” include plural referents unless the context clearly dictatesotherwise. Concentrations, amounts, and other numerical data may bepresented herein in a range format. It is to be understood that suchrange format is used merely for convenience and brevity and should beinterpreted flexibly to include not only the numerical values explicitlyrecited as the limits of the range, but also to include all theindividual numerical values or sub-ranges encompassed within that rangeas if each numerical value and sub-range is explicitly recited. Forexamples, a weight range of about 1 wt % to about 20 wt % should beinterpreted to include not only the explicitly recited concentrationlimits of 1 wt % to 20 wt %, but also to include individualconcentrations such as 2 wt %, 3 wt %, 4 wt %, and sub-ranges such as 5wt % to 15 wt %, 10 wt % to 20 wt %, etc. All percentages are by weight(wt %) unless otherwise indicated. As used herein, “image” refers tomarks, signs, symbols, figures, indications, and/or appearancesdeposited upon a material or substrate with either visible or aninvisible ink composition. Examples of an image can include characters,words, numbers, alphanumeric symbols, punctuation, text, lines,underlines, highlights, and the like.

When printing on fabric substrates, challenges exist due to the specificnature of fabric. Indeed, often, fabric does not accurately receiveinks. Some fabrics, for instance, can be highly absorptive, diminishingcolor characteristics, while some synthetic fabrics can be crystalline,decreasing aqueous ink absorption leading to ink bleed. Thesecharacteristics result in the image quality on fabric being relativelylow. Additionally, black optical density, color gamut, and sharpness ofthe printed images are often poor compared to images printed oncellulose paper or other media types. Durability, such as rubbingresistance, is another concern when printing on fabric, particularlywhen pigmented inks and ink compositions containing latex are used.Furthermore, when fabric is intended to be used in close proximity toindoor environments (as drapes, as overhead signage, as part offurnishings, or the like), there are concerns about flame resistance aswell as about using coatings that increase the flammability of thefabric. Thus, fire/flame resistance or inhibition characteristics arealso desirable when providing printable fabrics. Further, the softnessof the fabric printing media, also called “hands feeling”, is animportant and desirable feature. Treatments to the fabric base, such ascoating, is often used in order to make the media stiffer which canresults easily wrinkling and white line when material is folded orbended. In addition, from a manufacturer view-points, due the physicalstructure of fabric substrate (i.e. with high area open holes), thesolvent loss of coating composition, as called “de-watering effect”,often rises some challenges over other non-porous substrate like plasticfilm. The fabric print medium as described herein is able to solve allthese desirable features. The present disclosure is directed to a fabricprint medium that meet, to some extent, the features described above.

In one example, the present disclosure is drawn to a fabric print mediumcomprising a fabric base substrate; a barrier layer comprising awater-repellent agent and a physical gelling compound applied to, atleast, one side of the fabric base substrate; a primary coatingcomposition including a polymeric binder and filler particles, appliedon the fabric base substrate on the opposite side of the barrier layer;and an image-receiving coating composition including a first and asecond crosslinked polymeric network applied over the primary coatingcomposition. The present disclosure also relates to a method for formingsaid fabric print medium and to the printing method using said fabricprint medium. In another example, the present disclosure is drawn to animage-recoding medium comprising a fabric base substrate with a firstand a second side; a barrier layer comprising a hydrophobic compoundwith long paraffin chains and a physical gelling compound applied to oneside of the fabric base substrate; a primary coating compositionincluding a polymeric binder, filler particles and a flow-controllingagent, applied on the fabric base substrate, on the opposite side of thebarrier layer; and an image-receiving coating composition applied overthe primary coating composition.

The image printed on the fabric print medium of the present disclosureexhibits excellent printing qualities, durability and softness. By usingcoating compositions, in combination with fabric substrate, the printingprocess is more accurate and the printed image is more permanent. Theresultant printed fabric will also be able to provide fire/flameresistance or inhibition to the fabric. The present disclosure refers toa fabric print medium comprising a fabric base substrate and coatingcompositions applied to said fabric base substrate. The coatingcompositions, also called treatment compositions, once applied on thefabric base substrate, form thin layers onto the fabric base surface.

FIG. 1 illustrates the fabric print medium (100) as described herein.The fabric print medium (100) has two sides (101) and (102) and comprisea fabric base substrate (110), a barrier layer (120), a first coatingcomposition or primary coating composition (130) and a second coatingcomposition or image-receiving layer (140). As illustrated in FIG. 1,the fabric print medium (100) encompasses a fabric base substrate (110)with a barrier layer (120) that is applied on the opposite side of theprimary coating composition (130). An image-receiving layer (140) isdeposited over the primary coating composition (130). The primarycoating composition (130) and the image-receiving layer (140) areapplied to the image side (101) of the fabric print medium and thebarrier layer (120) is applied to the non-imaging side (102) (orbackside) of the fabric print medium.

An example of a method for forming a fabric print medium (200) inaccordance with the principles described herein, by way of illustrationand not limitation, is shown in FIG. 2. As illustrated in FIG. 2, suchmethod encompasses providing (210) a fabric base substrate (110) with afirst and a second sides; applying (220) a primary coating composition,including a polymeric binder and filler particles, on one side of thebase substrate; applying (220) a barrier layer (120) on the other sideof the fabric base substrate, opposing to primary layer; and applying animage-receiving coating composition including a first and a secondcrosslinked polymeric network, over the primary coating composition(240).

An example of a printing method in accordance with the principlesdescribed herein, by way of illustration and not limitation, is shown inFIG. 3. FIG. 3 illustrates examples of the printing method (300) thatencompasses providing a fabric print medium (310), applying an inkcomposition onto said a print medium (320) and obtaining a printedarticle (330).

The barrier layer (120) can be applied to the fabric substrate (110) ata variety of coat weights. In one example, the barrier layer (120) canbe applied to the fabric base substrate at a dry coat weight rangingfrom about 0.05 gram per square meter (g/m² or gsm) per side to about 5gram per square meter (g/m² or gsm) per side. In one other example, thebarrier layer (120) can be applied, to the fabric substrate, at a drycoat weight ranging from about 0.1 gram per square meter (g/m² or gsm)per side to about 3 gram per square meter (g/m² or gsm) per side. In yetanother example, the barrier layer (120) can be applied, to the fabricsubstrate, at a coating weight ranging from about 0.5 gsm to about 1.5gsm. Before applying barrier layer, the primary coating composition(130) is applied directly over the fabric substrate (110), on theopposite side of the barrier layer, at a dry coat weight ranging fromabout 5 gram per square meter (g/m² or gsm) per side to about 200 gramper square meter (g/m² or gsm), or at a dry coat weight ranging fromabout 10 gram per square meter (g/m² or gsm) to about 150 gram persquare meter (g/m² or gsm), or at a coating weight ranging from about 15gsm to about 50 gsm. The second coating composition or image-receivinglayer (140) can be applied, over the primary coating composition (130),at a dry coat weight ranging from about 0.5 gram per square meter (g/m²or gsm) per side to about 50 gram per square meter (g/m² or gsm). Thesecondary coating layer can be applied to the primary coatingcomposition at a thickness ranging from about 1 μm to about 50 μm.

The Fabric Base Substrate (110)

A fabric print medium (100) of the present disclosure, that can also becalled herein printable recording media, is a fabric media thatcomprises a fabric base substrate (110). The fabric base substrate (110)can also be called bottom supporting substrate or fabric supportingsubstrate. The word “supporting” also refers to a physical objective ofthe substrate that is to carry the coatings layer and the image that isgoing to be printed.

Regarding such fabric base substrate, any textile, fabric material,fabric clothing, or other fabric product where there is a desire forapplication of printed matter can benefit from the principles describedherein. More specifically, fabric substrates useful in presentdisclosure include substrates that have fibers that may be naturaland/or synthetic. The term “fabric” as used to mean a textile, a cloth,a fabric material, fabric clothing, or another fabric product. The term“fabric structure” is intended to mean a structure having warp and weftthat is one of woven, non-woven, knitted, tufted, crocheted, knotted,and pressured, for example. The terms “warp” and “weft” refers toweaving terms that have their ordinary means in the textile arts, asused herein, e.g., warp refers to lengthwise or longitudinal yarns on aloom, while weft refers to crosswise or transverse yarns on a loom.

It is notable that the term “fabric substrate” does not includematerials commonly known as any kind of paper (even though paper caninclude multiple types of natural and synthetic fibers or mixture ofboth types of fibers). The paper thereon is defined as the felted sheet,roll and other physical forms that are made of various plant fibers(like trees or mixture of plant fibers) with synthetic fibers by laiddown on a fine screen from a water suspension. Furthermore, fabricsubstrates include both textiles in its filament form, in the form offabric material, or even in the form of fabric that has been craftedinto finished article (clothing, blankets, tablecloths, napkins, beddingmaterial, curtains, carpet, shoes, etc.). In some examples, the fabricbase substrate has a woven, knitted, non-woven or tufted fabricstructure.

In some examples, the fabric base substrate comprises wool, cotton,silk, linen, jute, flax, hemp, rayon, corn starch, tapioca, sugarcane,polyvinyl chloride, polyester, polyamide, polyimide, polyacrylic,polyacrylic polypropylene, polyethylene, polyurethane, polystyrene,polyaramid, polytetrafluoroethylene, polyethylene terephthalate,fiberglass, polytrimethylene, polycarbonate, polyester terephthalate,polybutylene terephthalate, or a combination thereof. In some otherexamples, the fabric base substrate is woven, knitted, non-woven ortufted and comprises natural or synthetic fibers selected from the groupconsisting of wool, cotton, silk, rayon, thermoplastic aliphaticpolymers, polyesters, polyamides, polyimides, polypropylene,polyethylene, polystyrene, polytetrafluoroethylene, fiberglass,polycarbonates polytrimethylene terephthalate, polyethyleneterephthalate and polybutylene terephthalate. In yet some otherexamples, the fabric base substrate is a synthetic polyester fiber.

In some examples, the fabric base substrate (110) has a basis weightthat is ranging from about 50 gsm to about 400 gsm. In some otherexamples, the basis weight of the fabric substrate can range from about100 gsm to about 300 gsm.

The fabric base substrate can be a woven fabric where warp yarns andweft yarns are mutually positioned at an angle of about 90°. This wovenfabric includes, but is not limited to, fabric with a plain weavestructure, fabric with twill weave structure where the twill weaveproduces diagonal lines on a face of the fabric, or a satin weave. Thefabric base substrate can be a knitted fabric with a loop structureincluding one or both of warp-knit fabric and weft-knit fabric. Theweft-knit fabric refers to loops of one row of fabric are formed fromthe same yarn. The warp-knit fabric refers to every loop in the fabricstructure that is formed from a separate yarn mainly introduced in alongitudinal fabric direction. The fabric base substrate can also be anon-woven product, for example a flexible fabric that includes aplurality of fibers or filaments that are one or both of bonded togetherand interlocked together by a chemical treatment process (e.g., asolvent treatment), a mechanical treatment process (e.g., embossing), athermal treatment process, or a combination of two or more of theseprocesses.

The fabric base substrate can include one or both of natural fibers andsynthetic fibers. Natural fibers that may be used include, but are notlimited to, wool, cotton, silk, linen, jute, flax or hemp. Additionalfibers that may be used include, but are not limited to, rayon fibers,or those of thermoplastic aliphatic polymeric fibers derived fromrenewable resources, including, but not limited to, cornstarch, tapiocaproducts, or sugarcanes. These additional fibers can be referred to as“natural” fibers. In some examples, the fibers used in the fabric basesubstrate includes a combination of two or more from the above-listednatural fibers, a combination of any of the above-listed natural fiberswith another natural fiber or with synthetic fiber, a mixture of two ormore from the above-listed natural fibers, or a mixture of any thereofwith another natural fiber or with synthetic fiber.

The synthetic fiber that may be used in the fabric base substrate can bea polymeric fiber including, but not limited to, polyvinyl chloride(PVC) fibers, PVC-free fibers made of polyester, polyamide, polyimide,polyacrylic, polypropylene, polyethylene, polyurethane, polystyrene,polyaramid (e.g., Kevlar®) polytetrafluoroethylene (Teflon®) (bothtrademarks of E. I. du Pont de Nemours Company), fiberglass,polytrimethylene, polycarbonate, polyethylene terephthalate orpolybutylene terephthalate. In some examples, the fibers include acombination of two or more of the above-listed polymeric fibers, acombination of any of the above-listed polymeric fibers with anotherpolymeric fiber or with natural fiber, a mixture of two or more of theabove-listed polymeric fibers, or a mixture of any of the above-listedpolymeric fibers with another polymer fiber or with natural fiber. Insome examples, the synthetic fiber includes modified fibers fromabove-listed polymers. The term “modified fibers” refers to one or bothof the polymeric fiber and the fabric as a whole having underwent achemical or physical process such as, but not limited to, one or more ofa copolymerization with monomers of other polymers, a chemical graftingreaction to contact a chemical functional group with one or both thepolymeric fiber and a surface of the fabric, a plasma treatment, asolvent treatment, for example acid etching, and a biological treatment,for example an enzyme treatment or antimicrobial treatment to preventbiological degradation. The term “PVC-free” means no polyvinyl chloride(PVC) polymer or vinyl chloride monomer units in the substrate.

In some examples, the fabric base substrate contains both natural fiberand synthetic polymeric fiber. The amount of synthetic polymeric fiberscan represent from about 20% to about 90% of the total amount of fiber.The amount of natural fibers can represent from about 10% to about 80%of amount of fiber.

The fabric base substrate may further contain additives including, butnot limited to, one or more of colorant (e.g., pigments, dyes, tints),antistatic agents, brightening agents, nucleating agents, antioxidants,UV stabilizers, fillers and lubricants, for example. Alternatively, thefabric base substrate may be pre-treated in a solution containing thesubstances listed above before applying the coating composition. Theadditives and pre-treatments are included to improve various propertiesof the fabric.

The Barrier Layer Composition (120)

The fabric print medium of the present disclosure comprises a fabricbase substrate (110); a barrier layer (120), a primary coatingcomposition (130) and an image-receiving coating composition (140). Thebarrier layer (120) is applied directly on the fabric base substrate, onthe backside or non-imaging side of the media (102). The barrier layer(120) is applied on the opposite side of the primary coating composition(130). The barrier layer (120) is applied after the application of theprimary coating composition (130).

In one example, the barrier layer (120) can be applied to the fabricbase substrate at a dry coat weight ranging from about 0.05 gsm to about5 gsm per side. In one other example, the barrier layer (120) isapplied, to the fabric substrate, at a dry coat weight ranging fromabout 0.5 gsm to about 1.5 gsm.

When present on the fabric print medium, the barrier layer compositionacts as a barrier for aqueous liquid such as water, i.e. avoid thepenetration of the aqueous liquid into the fabric base substrate. Inaddition, it is believed that the presence of the barrier layer willprevent the “de-watering”effect that could happen during manufacture.Indeed, when printing of fabric substrate, due to the “open structure”of fabric substrate, solvent or water from coating compositions be lostby penetrating through the fabric base when apply coatings. Such a“de-watering” effect could become worse when apply image-receivingcoating on top of primary coating since capillary effect frommicroporous structure of the primary coating intensified the effect.Such “de-watering” effect could also rise the coating compositionviscosity which make very poor coating quality and which could alsodamage the coater.

The barrier layer composition is made of a chemical fluid that has athixotropic behavior. The thixotropic behavior refers to fluids that arenon-Newtonian fluids, i.e. which can show a time-dependent change inviscosity. The term “non-Newtonian” refers herein to fluid having aviscosity that is dependent on an applied force such as shear or thermalforces. For example, shear thinning fluids decrease in viscosity withincreasing rate of shear. The greater chemical fluid of the waterbarrier layer undergoes shear stress, the lower its viscosity will be.When the share stress is removed, the viscosity can be re-built up. Notbinding to any theory, it is believed, that such thixotropic behaviorreduces the penetration of the composition into the fabric substrate andhelps to retain the composition at the top surface of the substrate. Thefluid becomes thin under shear force when applied by a coatingapplication head (such as a blade coating head); when the fluid isdeposited (the nip of the blade and shear force are removed), theviscosity of fluid is re-built up and the fluid remains at top surfaceof the fabric substrate. Such thixotropic behavior allows the barrierlayer to stay only on the outmost depth of the opposite side of imageside to avoid any side effects such as decrease adhesion between imageside layers and fabric substrate.

Thus, in order to have such thixotropic behavior, the water barrierlayer comprises water-repellent agent, i.e. a chemical compound which isable reduce water penetration speed, and a physical gelling compound,i.e. a compound which is able to make physical network, as also calledphysical gelling, when reacting with the water-repellent chemical.

In some examples, the chemical fluid, or composition, which has athixotropic behavior and which forms the barrier layer, comprises themixture of water-repellent agent and physical gelling compound and is asolution having a pH which is adjusted in the range of about 8 to 10.

The barrier layer of the fabric print medium comprises thus awater-repellent agent and a physical gelling compound. The chemicalnature of the water-repellent agent will depend on the application ofthe barrier layer and of the primary coating composition on the media.The barrier layer (120) is applied over the fabric base substrate (110),on the opposite side of the primary and image-receiving layers. Anychemical compounds having water-repellency properties could be used as awater-repellent agent in the barrier layer of the media. Aswater-repellent property, it is meant herein that a layer formed withsuch compound will reduce the penetration speed of liquids (such aswater).

A water-repellent compound gives the surface containing it the abilityof reacting with water to cause it to move away, when exposed to it,instead of to be penetrated or soaked in. The water-repellent agent canbe a low surface energy chemical which has repelling capability toaqueous solvent, like water, and that reduces penetration of aqueoussolvent through the fabric base. After being applied the water-repellentagent may modify or improve the hydrophobicity of fabric substrate, orthe repelling strength the aqueous molecules. The water-repellent agentcan have the capability to form a continuous film-like structure, andcan form therefore a layer, or can form a non-continuous domainstructure randomly distributed on the surface of fabric substrate.

The water-repellent agent can be a hydrophobic compound or a mixture ofhydrophobic compounds, a mixture of hydrophobic with hydrophiliccompounds or lipophilic compounds, a mixture of lipophilic andhydrophilic compounds. In some examples, the water-repellent agent is ahydrophobic compound. The water-repellent agent can also be an organiccompound with different molecular groups with low mole concentration ofhydrophilic group and high mole concentration of hydrophobic group inthe molecule to balance various performances. The hydrophilic group ofthe water-repellent agent may carry a negative or positive charge, bothpositive and negative charges or no charge at all. The water-repellentagent can be, for example, a polyethylene or polyethylene oxide reactionproduct with acids, alcohols phenols and amines and other copolymerssuch as polyethylene glycol polyester copolymer. Such compounds arecommercially available, for example, under the Tradename Sorez® 100supplied by Ashland Co.

In some examples, the water-repellent agent is a compound with longparaffin chains. Compounds with long paraffin chains have a molecularstructure of long alkane chain, i.e. alkane of the formula CnHn+2 wheren is equal or superior to 6. In some examples, the water-repellent agentis a hydrophobic compound with long paraffin chains. In some otherexamples, the water-repellent agent is a hydrophobic compound with longparaffin chains having the formula CnHn+2 where n is equal or superiorto 6.

Without being linked by any theory, it is believed that long paraffinchains (long chain hydrocarbons or alkanes) can wrap themselvesspiral-like around individual fibers, filaments or yarns in a very finefilm. It is believed that these long paraffin chains (long chainalkanes) reduce the surface tension so that water penetration speed canbe reduced. The water-repellent agents with long paraffin chains can behalogen containing like fluorine containing chemicals (afluoro-containing polymeric substance) or halogen-free chemicals likefree chlorine or fluorine chemicals. In some examples, thewater-repellent agents with long paraffin chains are halogen containingchemicals like fluorine containing chemicals. Such halogen-containingpolymeric substance contains a halogenic carbon chain in linear,branched chain, and cyclic chain structure and halogenic-siliconecopolymers. For example, more than 30 wt % of fluorine can be includedinto the polymer chain in view of achieving optimized effect, and theend groups of the polymer chain can be fluorinated.

Examples of water-repellent agent include, but are not limited to,polyvinylidene chloride emulsion, polyolefin emulsion,poly(ethyl-terephthalate) emulsion, aqueous wax dispersion, emulsion ofa hydrogen siloxane, polyalkylene oxide block co-polymers emulsion,polyglycerol esters, poly-oxy-alkylene polyol esters, poly alkylglucosides, perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid(PFOA). Other examples include also shorter perfluoro-alkyl chainderivatives such as poly(fluorooxetane), acrylate-modifiedpoly(fluorooxetane), alkyl-dimethylamine oxide, polyoxyethylene alkylether, alkyl-trimethyl-ammonium salts, alkyl-benzene sulphonate, alkyldiphenyl-oxide disulphonates, C₁₄-C₁₈ α-olefin sulphonates paraffinsulphonates alkyl sulphates, alkyl ether sulphates, alkyl secondaryamines, polymeric alkyl phenol ethoxylates, and fatty alcoholethoxylates. The barrier layer can comprise a water-repellent agent thatis selected from the group consisting of polyvinylidene chlorideemulsion, polyolefin emulsion, poly(ethyl-terephthalate) emulsion,aqueous wax dispersion, perfluorooctane sulfonate (PFOS),perfluorooctanoic acid (PFOA) and emulsion of a hydrogen siloxane.

In some examples, the water-repellent agent with long paraffin chainscan be halogen or fluorine free long chain hydrocarbons, such ascommercial compounds available under the tradename Baygard® WRS (fromTanatex Chemicals) or Ecorepel® (from Scholler technology). In someother examples, the water-repellent agents are fluorine-freepoly(meth)acrylate. In some other examples, the water-repellent agentsencompass, at least, a self-cross-linkable polymeric hydrophobicsubstance in an emulsion form and, at least, a surfactant.

The barrier layer comprises a water-repellent agent and physical gellingcompound. The physical gelling compound is capable to make a physicalnetwork with the water-repellent agent. The physical gelling compoundwill be able to generate various physical force, or physical bonding,with the water-repellent agent to form a gel-like solution. By “gel-likesolution”, it is meant herein a solution system that has a low solidscontent, (i.e. from about 5 to about 30 wt %) but very high viscosity(i.e. above 15,000 cps at 30 rpm when measure by a Brookfieldviscometer, at 25° C.), at low share stress and that will behave like anon-flowable semi-solids gel. This “gel-like solution” will be able to“de-bonding” at higher share force and yield a low viscosity fluidrefereed as thixotropic behavior described previously.

The physical gelling compounds are high molecular weight polymers, i.e.having a molecular weight ranging from about 300,000 to about 1,000,000.The physical gelling can be copolymers of acrylates, copolymers withacrylate based polyelectrolyte backbone, copolymers with polyesterbackbone, or copolymers with polyurethane based copolymer backbone. Insome examples, the physical gelling compound is selected from the groupconsisting of copolymers of acrylates, copolymers with acrylate basedpolyelectrolyte backbone, copolymers with polyester backbone, andcopolymers with polyurethane based copolymer backbone.

In some examples, the physical gelling compound, which is part of thebarrier layer, is high molecular weight copolymers of acrylates (i.e.having a molecular weight ranging from about 300,000 to about 1,000,000)such as copolymer of methacrylic acid and ethyl acrylate ester. Examplesof such compounds include Acusol® 810A, Acusol L® 830, Acusol® 835,ACUSOL® 842 (supplied by Rohm Haas/Dow Co); or Alcogum® L11, Alcogum®L12, Alcogum® L51, Alcogum® L31 and Alcogum® L52 (available from AkzoNobel Co).

In some other examples, the physical gelling compound of the barrierlayer is high molecular weight copolymers with acrylate basedpolyelectrolyte backbone. Such high molecular weight copolymers withacrylate based polyelectrolyte backbone can be, for examples, acrylateacid copolymers, grafted pendant with long-chain hydrophobic groups inaddition to acid groups in backbone distributed throughout the polymerchain. Examples of such polymers that are commercially available includeTexicryl® 13-317, Texicryl® 13-313, Texicryl® 13-308, and Texicryl®13-312 (all available from Scott Bader Group).

In yet some other examples, the physical gelling compound of the barrierlayer, is high molecular weight copolymers with polyester backbone. Suchhigh molecular weight copolymers with polyester backbone can be, forexamples, polyethylene glycol copolymers, grafted pendant withlong-chain hydrophobic groups in addition to polar groups in backbonedistributed throughout the polymer chain. Examples of such polymers thatare commercially available include Rheovis® PE from BASF. In furtherexamples, the physical gelling compound of the barrier layer is highmolecular weight copolymers with polyurethane based copolymer backbone.Such high molecular weight copolymers with polyurethane based copolymerbackbone can be, for examples, as polyethylene glycol and isophoronediisocyanate, which can be end-capped with long-chain alkanol inaddition to backbone distributed throughout the polymer chain. Examplesof such polymers that are commercially available include Acusol® 880,Acusol® 882 (from Rohm Haas).

The Primary Coating Composition (130)

The fabric print medium of the present disclosure comprises a fabricbase substrate (110), a barrier layer (120) comprising a water-repellentagent and a physical gelling compound, a primary coating composition(130) and an image-receiving coating composition (140). The primer orprimary coating composition (130), is applied to one side of the fabricbase substrate (110), and is based on a treatment composition thatincludes at least a polymeric binder and filler particles. The primarycoating composition (130) is directly applied on the fabric substrate(110) on the image side (101) of the media and the other side, orbackside (102), of the fabric bas substrate is coated with the barrierlayer (120).

The primary coating composition or primary coating layer includes apolymeric binder and filler particles applied. The primary coatingcomposition can also include a flame-retardant agent or filler particleswith flame retardancy properties. Other functional additives can beadded to the primary coating composition, for specific property controlsuch as, for examples, optical brightener agent, optical brighteneragent carrier, dyes for color hue, surfactant for wettability, andprocessing control agent such as deformer, and PH control base/acidbuffer.

The primary coating composition (130) contains a polymeric binder.Without being linked by any theory, it is believed that the polymericbinder can provide binding function to the fillers to form a continuouslayer and adhesion function between coating layers and the fabricsubstrate. In other examples, the polymeric binder can provide blockingfunctions to prevent the printing ink from penetrating into thez-direction of the fabric substrate so that a high ink volume in kept onthe surface of printing media to ensure a vivid image.

The polymeric binder can be present, in the primary coating composition,in an amount ranging from about 10 wt % to about 95 wt % by total weighof the primary coating composition. In one example, the polymeric bindercan range from about 45 wt % to about 94 wt % of the primary coatingcomposition. In another example, the polymeric binder can range fromabout 10 wt % to about 80 wt % of the primary coating composition. Inyet another example, the polymeric binder can range from about 20 wt %to about 88 wt % of the primary coating composition.

The polymeric binder can be either water a soluble, a synthetic or anatural substance or an aqueous dispersible substance like polymericlatex. In some other examples, the polymeric binder is polymeric latex.The polymeric binder can be a water-soluble polymer or water dispersiblepolymeric latex. In some examples, the polymeric binder has a glasstransition temperature (Tg) that is less than 5° C. Indeed, it isbelieved that polymeric binder with higher glass transition temperature(Tg) might contribute to a stiff coating and can damage the fabric “handfeeling” of the printing media. In some examples, the polymeric bindershave a glass transition temperature (Tg) ranging from −40° C. to 0° C.In some other examples, the polymeric binders have a glass transitiontemperature (Tg) ranging from −20° C. to −5° C. The way of measuring theglass transition temperature (Tg) parameter is described in, forexample, Polymer Handbook, 3rd Edition, authored by J. Brandrup, editedby E. H. Immergut, Wiley-Interscience, 1989.

In some examples, the polymeric binders are crossed-linked binder.“Crossed-linked binder” refers to the fact that multiple polymersubstances with reactive function groups can react with each other toform a between-molecular chain structure, a cross linker, amacro-molecular substance or a low molecular weight chemical with morethan two function groups that can be used. Binders with “self-crosslink”capability can mean that macro-molecular chains have different reactivefunction groups that can be used. The cross-linked binders can balanceboth softness and mechanical strength of the coating layers.

Suitable polymeric binders include, but are not limited to,water-soluble polymers such as polyvinyl alcohol, starch derivatives,gelatin, cellulose derivatives, acrylamide polymers, and waterdispersible polymers such as acrylic polymers or copolymers, vinylacetate latex, polyesters, vinylidene chloride latex, styrene-butadieneor acrylonitrile-butadiene copolymers. Non-limitative examples ofsuitable binders include styrene butadiene copolymer, polyacrylates,polyvinylacetates, polyacrylic acids, polyesters, polyvinyl alcohol,polystyrene, polymethacrylates, polyacrylic esters, polymethacrylicesters, polyurethanes, copolymers thereof, and combinations thereof. Insome examples, the binder is a polymer or a copolymer selected from thegroup consisting of acrylic polymers or copolymers, vinyl acetatepolymers or copolymers, polyester polymers or copolymers, vinylidenechloride polymers or copolymers, butadiene polymers or copolymers,styrene-butadiene polymers or copolymers and acrylonitrile-butadienepolymers or copolymers. In a further example, the polymeric binder caninclude an acrylonitrile-butadiene latex.

In some other examples, the binder component is a latex containingparticles of a vinyl acetate-based polymer, an acrylic polymer, astyrene polymer, an SBR-based polymer, a polyester-based polymer, avinyl chloride-based polymer, or the like. In yet some other examples,the binder is a polymer or a copolymer selected from the groupconsisting of acrylic polymers, vinyl-acrylic copolymers andacrylic-polyurethane copolymers. Such binders can be polyvinylalcohol orcopolymer of vinylpyrrolidone. The copolymer of vinylpyrrolidone caninclude various other copolymerized monomers, such as methyl acrylates,methyl methacrylate, ethyl acrylate, hydroxyethyl acrylate, hydroxyethylmethacrylate, ethylene, vinylacetates, vinylimidazole, vinylpyridine,vinylcaprolactams, methyl vinylether, maleic anhydride, vinylamides,vinylchloride, vinylidene chloride, dimethylaminoethyl methacrylate,acrylamide, methacrylamide, acrylonitrile, styrene, acrylic acid, sodiumvinylsulfonate, vinylpropionate, and methyl vinylketone, etc. Examplesof binders include, but are not limited to, polyvinyl alcohols andwater-soluble copolymers thereof, e.g., copolymers of polyvinyl alcoholand poly(ethylene oxide) or copolymers of polyvinyl alcohol andpolyvinylamine; cationic polyvinyl alcohols; aceto-acetylated polyvinylalcohols; polyvinyl acetates; polyvinyl pyrrolidones includingcopolymers of polyvinyl pyrrolidone and polyvinyl acetate; gelatin;silyl-modified polyvinyl alcohol; styrene-butadiene copolymer; acrylicpolymer latexes; ethylene-vinyl acetate copolymers; polyurethane resin;polyester resin; and combination thereof.

In one example, the polymeric binder may have an average molecularweight (Mw) of about 5,000 to about 200,000. In another example, theaverage molecular weight of the polymeric binder can vary from 10,000 Mwto about 200,000 Mw. In yet another example, the average molecularweight of the polymeric binder can vary from 20,000 Mw to 100,000 Mw. Ina further example, the average molecular weight of the polymeric bindercan vary from 100,000 Mw to 200,000 Mw. In one example, the polymericbinder can have a weight average molecular weight from 5,000 Mw to200,000 Mw and can include polystyrene-butadiene emulsion, acrylonitrilebutadiene latex, starch, gelatin, casein, soy protein polymer,carboxy-methyl cellulose, hydroxyethyl cellulose, acrylic emulsion,vinyl acetate emulsion, vinylidene chloride emulsion, polyesteremulsion, polyvinyl pyrroilidene, polyvinyl alcohol, styrene butadieneemulsions, or combination thereof.

In some examples, the polymeric binder is a self-crosslinking aqueousacrylic dispersion such an Edolan® AB available from Tanatex Chemicals(having a solids content of 45% and Tg of −18° C.).

The primary coating composition (130) contains a polymeric binder andfiller particles. The filler particles can include inorganic powder,inorganic mineral powder, organic powder and mixture of the both. Insome examples, the fillers are particles that can include calciumcarbonate, kaolin, talc, calcium sulfate, barium sulfate, titaniumdioxide, zinc oxide, zinc sulfide, zinc carbonate, satin white, aluminumsilicate, diatomite, calcium silicate, magnesium silicate, silica,amorphous silica, synthetic amorphous silica, colloidal silica, alumina,colloidal alumina, boehmite, pseudo-boehmite, aluminum hydroxide,aluminum, lithopone, zeolite, magnesium carbonate, magnesium hydroxide,magnesium, calcium, clay, calcium carbonate, polystyrene,polymethacrylates, polyacrylates, polyolefins, polyethylene,polypropylene, copolymers, and combinations thereof. In some otherexamples, the filler particles can include calcium carbonate. Thecalcium carbonate can be in the form of ground calcium carbonate,precipitated calcium carbonate, modified forms thereof, and combinationsthereof. In another example, the filler particles can include calciumcarbonate and clay.

In some examples, the primary coating composition (130) contains fillerparticles that have a nature of flame retardancy (or flame retardancyproperties) or contains fillers and, separately, a flame-retardantagent. The fillers that have a nature of flame retardancy or flameretardancy properties can be considered as flame-retardant agents. Asflame-retardant agent, it is meant herein any substance that inhibits orreduces flammability or delays their combustion of the media containingit.

In some examples, the “fillers” can be solid particles in the roomtemperature having flame retardancy properties. In some other examples,the “fillers” also refers to the solid powder package that include asolid powder in the room temperature which has lower or limited flameretardancy properties in one example, or has no capability of flameretardancy properties in another example. In this case, the “fillerpackage” or also called “filler”, comprises a solid particle compoundsand a flame-retardant agent either in solid or liquid state in roomtemperature. The examples of fillers are, for example, but not limitedto, an organo-halogenated compound, a polymeric brominated compound, ametal oxide and phosphorus containing composition, a phosphorus andhalogen containing composition, a phosphorus continuing composition, anitrogen containing composition, a halogen, an organophosphate, or acombination thereof.

In one example, the fillers with flame retardancy properties can includea mineral compound. Exemplary mineral compounds can include aluminumhydroxide, magnesium hydroxide, huntite (magnesium calcium carbonate),hydromangesite (hydrated magnesium carbonate), phosphorus, redphosphorus, boehmite (aluminum oxide hydroxide), boron compounds, orcombinations thereof. In another example, the flame-retardant in fillerpackage can include either a liquid or a solid flame-retardant such asorganohalogenated compound. Exemplary organohalogenated compounds caninclude organobromines, organochlorines, decabromodiphenyl ether,decabromodiphenyl ethane, and combinations thereof.

In yet another example, either the filler or the flame-retardant caninclude a polymeric brominated compound. Exemplary polymeric brominatedcompounds can include brominated polystyrenes, brominated carbonateoligomers, brominated epoxy oligomers, tetrabro-mophthalic anhydride,tetrabromo-bisphenol A, hexabromocyclododecane, chlorendic acid, ethersof chlorendic acid, chlorinated paraffins, and combinations thereof. Inyet another example, either the filler or flame-retardant can include ametal and phosphorus containing composition. Example metal andphosphorus containing compositions can include aluminumdiethylphosphinate, calcium diethylphosphinate, and combinationsthereof. In a further example, either the filler or the flame-retardantcan include a phosphorus and a halogen containing composition. Exemplaryphosphorus and halogen containing compositions can includetris(2,3-dibromopropyl) phosphate, chlorinated organophosphates,tris(1,3-dichloro-2-propyl) phosphate, tetrekis(2-chloroethyl)dicloro-isopentyldiphosphate, tris (1,3-dichloroisopropyl) phosphate,tris(2-chloroisopropyl) phosphate, and combinations thereof.

In some example, either the filler or the flame-retardant can include aphosphorus containing composition. Exemplary phosphorus containingcompositions can include phosphates, phosphonates, phoshpinates, andcombinations thereof. In some examples, the phosphorus containingcomposition can have different oxidations states. In one example, thephosphorus containing composition can be a closed ring structure such asFR-102® (available from Shanghai Xusen Non-Halogen Smoke SuppressingFire Retardants Co. Ltd, China) and Aflammit® (available from Thor,Germany). In another example, the phosphorus containing composition canbe a water-soluble phosphorus containing compound. Exemplarywater-soluble phosphorus containing compositions can include, aphosphonate ester with one or two, closed 4 to 6 member phosphoruscontaining ring structures. In one example, the water-soluble phosphoruscontaining composition can be5-ethyl-2-methyl-1,3,2-dioxaphosphoranian-5-yl)methyl dimethylphosphonate P oxide. In another example, the water-soluble phosphoruscontaining composition can bebis[(-ethyl-2-methyl-1,3,2-dioxaphosphorinan-5-yl)methyl] methylphosphonate P,P′-dioxide. In another example, either the filler or theflame-retardant can include a nitrogen containing composition. Exemplarynitrogen containing compositions can include melamines, melaminederivatives, melamine, melamine cyanurate, melamine polyphosphate, melem(heptazine derivative), melon (heptazine derivative), and combinations.

In some examples, either the filler or the flame-retardant can be acombination of a phosphorus containing compound, a nitrogen containingcompound, and/or a halogen. In one example, the flame-retardant caninclude a phosphorus and a nitrogen containing composition. Exemplaryphosphorus and nitrogen containing compositions can include ammoniumpolyphosphate (APP), poly 4,4-diaminodiphenyl methane spirocyclicpentaerythritol bisphosphonate (PDSPB), 1,4-di(diethoxy thiophosphamidebenzene (DTPAB), and combinations. In another example, either the filleror the flame-retardant can include an organophosphate. Theorganophosphate can include aliphatic phosphate; aliphatic phosphonate;aromatic phosphonate; aliphatic organophosphate; aromaticorganophosphate; polymeric organophosphate with 2 or 3 oxygen atomsattached to the central phosphorus and combinations.

In some examples, the flame-retardant agents or the filler particleswith flame retardancy properties are selected from the group consistingof phosphorus-containing compounds, nitrogen-containing compounds,organophosphate compounds, alumina trihydrate and calcium carbonate. Insome other examples, the filler particles with flame retardancyproperties are selected from the group consisting ofphosphorus-containing compounds, nitrogen-containing compounds,organophosphate compounds, alumina trihydrate and calcium carbonate. Inyet some other examples, the flame-retardant agents or the fillerparticles with flame retardancy properties are selected from the groupconsisting of phosphorus-containing compounds and nitrogen-containingcompounds. The flame-retardant, either in solid state or in liquidstate, can also be selected from the group consisting ofphosphorus-containing compounds, nitrogen-containing compounds,organophosphate compounds, alumina trihydrate and calcium carbonate.

Examples of commercially available products, with flame retardancyproperties and the flame-retardant either in solid state or in liquidstate include FR102® (available from Shanghai Xusen Co Ltd) or Aflammit®PE and Aflammit® MSG (both available from Thor), Exolit® AP compounds(available from Clariant), solid Aflammit® powder compounds (availablefrom Thor), Disflamoll® DPK (available from Lanxess), Phoslite Bcompounds (available from Italmatch Chemicals), or SpaceRite® S-3 (J.M.Huber Corp).

In some examples, the filler or filler package or filler particles withflame retardancy properties or flame-retardant agent is present, in theprimary coating composition (130), in an amount representing from about10 to about 90 wt % by total weigh of the primary coating composition.In some other examples, the filler or filler package or flame-retardantagent is present, in the primary coating composition (130), in an amountrepresenting from about 5 wt % to about 90 wt %, or from about 10 wt %to about 80 wt %, or from about 15 wt % to about 70 wt %, by total weighof the primary coating composition.

The filler or the filler package can include a mineral powder, anorgano-halogenated compound, a polymeric brominated compound, a metaland phosphorus containing composition, a phosphorus containingcomposition, a nitrogen containing composition, a halogen, anorganophosphate, or combination thereof.

In some examples, in “filler package”, the ratio of filler particles toflame-retardant agent can vary from about 2 to about 35 by dry weight.In some other examples, the ratio of filler particles to flame-retardantagent can range from 3 to about 20 by dry weight. In yet some otherexamples, the ratio of filler particles to flame-retardant agent canrange from about 5 to about 15. The size of the filler particles canalso vary. In one example, the filler particles can have an averageparticle size ranging from about 0.1 μm to about 20 μm. In anotherexample, the filler particles can have an average particle size rangingfrom about 0.2 μm to about 18 μm. In yet another example, the fillerparticles can have an average particle size ranging from about 0.5 μm toabout 10 μm. In a further example, the filler particles can have anaverage particle size ranging from about 1 μm to about 5 μm. The fillerparticles can include from 5 wt % to about 95 wt % of the primarycoating composition based on dry weight of the primary coatingcomposition and can have an average particle size from 0.1 μm to 20 μm.The filler particles can be added to the primary coating composition inthe form of a dry powder, dispersed in a slurry, or in the form of anaqueous suspension.

In some examples, the primary coating may also comprise aflow-controlling agent, where the “flow-controlling agent” refers to achemical compound, or mixture of the compounds which can adjustrheological behavior of the coating composition before drying.Rheological behavior refers to the properties related to flowing andleveling of the coating composition. In some examples, theflow-controlling agent can increase viscosity and reduce flowing ofcoating composition and made even levelling of coating compositionbefore drying by use of physical force to expanding the distance ofmolecules.

In some examples, the flow-controlling agent is a modifiedpolysaccharide compound like starch thickener and chemicals made byesterification or etherification of cellulose. For example, but notlimited to, the flow-controlling agent can be hydroxyethylcellulose(HEC), methyl-hydroxyethyl cellulose(MHEC), ethyl-hydroxyethylcellulose(EHEC) or carboxy-methyl cellulose (CMC). The molecular weightof these modified polysaccharides can be in the range of about 500,000to 1,000,000. Commercially flow-controlling agents are available, forexample, under the trade names Natroso, Culminal, Klucel and Blanosefrom Hercules Co.

In some examples, the flow-controlling agent is a physical gellingcompound as described above. The flow-controlling agent is a physicalgelling compound which can be the same or different form the physicalgelling agents present in the barrier layer. For example, it can beselected from the group consisting of copolymers of acrylates,copolymers with acrylate based polyelectrolyte backbone, copolymers withpolyester backbone, and copolymers with polyurethane based copolymerbackbone.

The primary coating composition is applied first directly over thefabric substrate and the barrier layer is applied on the opposite sideof primary coating composition. If the barrier layer is being appliedfirst, the water repelling component might possibly migrated on thesurface where primary coating is deposited, and might cause very pooradhesion, which would accordingly damage the printing image durability,when the primary coating composition is applied prior to barrier layer,it will reduce the possibly penetration of primary coating compositioninto the open fabric substrate. No bonded to any theory, it is believedthat the flow-controlling agent will help turning the primary coatingcomposition into a rheology with pseudo-plastic and thixotropic flowbehavior (where the viscosity is high under the low stress while it willreduce with high share stress). In some examples, after adding theflow-controlling agent, the viscosity of the primary coating compositionis ranged from about 4,000 cps to about 30,000 cps under the spindlespeed of 100 rpm using a Brookfield viscometer, when measured at 25° C.

The Image-Receiving Layer (140)

The fabric print medium (100) of the present disclosure includes animage-receiving layer (140). The image-receiving layer (140), or inkjetreceiving layer, will form a coating layer and is applied over theprimary coating composition (130) on the fabric base substrate (110).The image-receiving layer would act as the image-receiving layer since,during the printing process, the ink will be directly deposited on itssurface.

In some examples, the image-receiving coating composition is applied tothe primary coating composition at a coat weight ranging from about 0.1to about 40 gsm (gram per square meter) or at a coat weight ranging orfrom about 1 to 20 gsm (gram per square meter). In some other examples,the image-receiving coating composition is applied to the primarycoating composition at a thickness ranging from about 1 μm to about 50μm with a dry coat weight ranging from about 0.5 gsm to about 50 gsm.

In some examples, the image-receiving layer includes a first and asecond crosslinked polymeric network. The wording “polymer network”refers herein to a polymer and/or a polymer mixture which can beself-cross-linked, by reaction of different function groups in the samemolecular chain, or inter-cross-linked by reaction with another compoundwhich has different function group. In some other examples, theimage-receiving layer includes a first and a second polymeric network.In yet some other examples, the image-receiving layer includes a firstand a second polymeric network that are crosslinked polymeric network.The first crosslinked polymeric network and the second crosslinkedpolymeric network can be either different or identical by their chemicalnatures.

The image-receiving layer (140) comprises a first crosslinked polymericnetwork and a second crosslinked polymeric network. In some examples,the image-receiving layer comprises a first crosslinked polymericnetwork, a second crosslinked polymeric network, and filler particles.The filler particles can be inorganic filler particles, organicparticles, particles with or without flame retardancy nature, andflame-retardants. The filler particles can be the same or different asthe one used in the primary coating composition as described previously.

In some examples, the first crosslinked polymeric network can becrosslinked to itself. In another example, the first crosslinkedpolymeric network can be crosslinked to itself and to the secondcrosslinked polymeric network. In one example, the second crosslinkedpolymeric network can be crosslinked to itself. When the firstcrosslinked polymeric network and the second crosslinked polymericnetwork are not crosslinked to one another they can be entangled orappear layered onto one another.

The first and second crosslinked polymeric networks can be present inthe secondary coating layer in a variety of amounts. The first andsecond crosslinked polymeric networks can collectively represent fromabout 80 wt % to about 99 wt % of the total weight of theimage-receiving layer. In another example, the first and secondcrosslinked polymeric networks can collectively represent from about 85wt % to about 95 wt % of the total weight of the image-receiving layer.In a further example, the first and second crosslinked polymericnetworks can collectively range from about 85 wt % to about 93 wt % ofthe total weight of the image-receiving layer. In some examples, thefirst and second crosslinked polymeric networks can be present in equalamounts. In other examples, the first and second crosslinked polymericnetworks can be present in different amounts.

In some examples, in the image-receiving coating composition, the firstcrosslinked polymeric network and the second crosslinked polymericnetwork are different and independently comprises polyacrylate,polyurethane, vinyl-urethane, acrylic urethane, polyurethane-acrylic,polyether polyurethane, polyester polyurethane, polycaprolactampolyurethane, polyether polyurethane, alkyl epoxy resin, epoxy novolacresin, polyglycidyl resin, polyoxirane resin, polyamine, styrene maleicanhydride, a derivative thereof, or a combination thereof. The firstand/or the second crosslinked polymeric networks can include apolyacrylate, polyurethane, vinyl-urethane, acrylic urethane,polyurethane-acrylic, polyether polyurethane, polyester polyurethane,polycaprolactam polyurethane, polyether polyurethane, alkyl epoxy resin,epoxy novolac resin, polyglycidyl resin, polyoxirane resin, polyamine,styrene maleic anhydride, derivative thereof, or combination thereof. Insome examples, the first and second crosslinked polymeric networks canbe different polymers.

In one example, the first and/or the second crosslinked polymericnetwork can include a polyacrylate based polymer. Exemplary polyacrylatebased polymers can include polymers made by hydrophobic additionmonomers include, but are not limited to, C₁-C₁₂ alkyl acrylate andmethacrylate (e.g., methyl acrylate, ethyl acrylate, n-propyl acrylate,isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butylacrylate, tert-butyl acrylate, 2-ethylhexyl acrylate, octyl arylate,methyl methacrylate, ethyl methacrylate, n-propyl methacrylate,isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate,sec-butyl methacrylate, tert-butyl methacrylate), and aromatic monomers(e.g., styrene, phenyl methacrylate, o-tolyl methacrylate, m-tolylmethacrylate, p-tolyl methacrylate, benzyl methacrylate), hydroxylcontaining monomers (e.g., hydroxyethylacrylate,hydroxyethylmthacrylate), carboxylic containing monomers (e.g., acrylicacid, methacrylic acid), vinyl ester monomers (e.g., vinyl acetate,vinyl propionate, vinylbenzoate, vinylpivalate, vinyl-2-ethylhexanoate,vinylversatate), vinyl benzene monomer, C₁-C₁₂ alkyl acrylamide andmethacrylamide (e.g., t-butyl acrylamide, sec-butyl acrylamide,N,N-dimethylacrylamide), crosslinking monomers (e.g., divinyl benzene,ethyleneglycoldimethacrylate, bis(acryloylamido)methylene), andcombinations thereof. Polymers made from the polymerization and/orcopolymerization of alkyl acrylate, alkyl methacrylate, vinyl esters,and styrene derivatives may also be useful. In one example, thepolyacrylate based polymer can include polymers having a glasstransition temperature greater than 20° C. In another example, thepolyacrylate based polymer can include polymers having a glasstransition temperature of greater than 40° C. In yet another example,the polyacrylate based polymer can include polymers having a glasstransition temperature of greater than 50° C.

In some examples, the first and/or the second crosslinked polymericnetwork can be formed by using self-cross linked polyurethane polymersor cross-linkable polyglycidyl or polyoxirane resins. In some otherexamples, the first and/or second crosslinked polymeric network can beformed by using self-cross linked polyurethane polymers. The self-crosslinked polyurethane polymer can be formed by reacting an isocyanate witha polyol. Exemplary isocyanates used to form the polyurethane polymercan include toluenediisocyanate, 1,6-hexamethylenediisocyanate,diphenylmethanediisocyanate, 1,3-bis(isocyanatemethyl)cyclohexane,1,4-cyclohexyldiisocyanate, p-phenylenediisocyanate,2,2,4(2,4,4)-trimethylhexamethylenediisocyanate,4,4′-dicychlohexylmethanediisocyanate, 3,3′-dimethyldiphenyl,4,4′-diisocyanate, m-xylenediisocyanate, tetramethylxylenediisocyanate,1,5-naphthalenediisocyanate,dimethyl-triphenyl-methane-tetra-isocyanate,triphenyl-methane-tri-isocyanate, tris(iso-cyanate-phenyl)thiophosphate,and combinations thereof. Commercially available isocyanates can includeRhodocoat® WT 2102 (available from Rhodia AG, Germany), Basonat® LR 8878(available from BASF Corporation, N. America), Desmodur® DA, andBayhydur® 3100 (Desmodur® and Bayhydur® are available from Bayer AG,Germany). In some examples, the isocyanate can be protected from water.Exemplary polyols can include 1,4-butanediol; 1,3-propanediol;1,2-ethanediol; 1,2-propanediol; 1,6-hexanediol;2-methyl-1,3-propanediol; 2,2-dimethyl-1,3-propanediol; neopentylglycol; cyclo-hexane-dimethanol; 1,2,3-propanetriol;2-ethyl-2-hydroxymethyl-1,3-propanediol; and combinations thereof. Insome examples, the isocyanate and the polyol can have less than threefunctional end groups per molecule. In another example, the isocyanateand the polyol can have less than five functional end groups permolecule. In yet another example, the polyurethane can be formed from apolyisocyanate having at least two isocyanate functionalities and apolyol having at least two hydroxyl or amine groups. Exemplarypolyisocyanates can include diisocyanate monomers and oligomers. Theself-cross linked polyurethane polymer can also formed by reacting anisocyanate with a polyol, where both isocyanates and polyols haveaverage less than three end functional groups per molecule so that thepolymeric network is based on a liner polymeric chain structure.

The polyurethane chain can have a trimethyloxysiloxane group andcross-link action can take place by hydrolysis of the function group toform silsesquioxane structure. The polyurethane chain can also have anacrylic function group, and the cross-link structure can be formed bynucleophilic addition to acrylate group through acetoacetoxyfunctionality. In some other examples, the first and/or secondcrosslinked polymeric network is formed by using vinyl-urethane hybridcopolymers or acrylic-urethane hybrid polymers. In yet some otherexamples, the polymeric network includes an aliphaticpolyurethane-acrylic hybrid polymer. Representative commerciallyavailable examples of the chemicals which can form a polymeric networkinclude, but are not limited to, NeoPac® R-9000, R-9699 and R-9030 (fromZeneca Resins), Sancure® AU4010 (from Lubrizol) and Hybridur® 570 (fromAir Products).

In one example, the weight average molecular weight of the polyurethanepolymer used in the first and/or second crosslinked polymer can rangefrom about 20,000 Mw to about 200,000 Mw as measured by gel permeationchromatography. In another example, the weight average molecular weightof the polyurethane polymer can range from about 40,000 Mw to about180,000 Mw as measured by gel permeation chromatography. In yet anotherexample, the weight average molecular weight of the polyurethane polymercan range from about 60,000 Mw to about 140,000 Mw as measured by gelpermeation chromatography.

Exemplary polyurethane polymers can include polyester basedpolyurethanes, U910, U938 U2101 and U420; polyether based polyurethane,U205, U410, U500 and U400N; polycarbonate based polyurethanes, U930,U933, U915 and U911; castor oil based polyurethane, CUR21, CUR69, CUR99and CUR991; and combinations thereof (These polyurethanes are availablefrom Alberdingk Boley Inc., North Carolina, USA).

The polymeric network (the first and/or second) can include a polymericcore that is, at least, one polyurethane. The polyurethanes includealiphatic as well as aromatic polyurethanes. The polyurethane istypically the reaction products of the following components: apolyisocyanate having at least two isocyanate functionalities (—NCO) permolecule with, at least, one isocyanate reactive group such as a polyolhaving at least two hydroxy groups or an amine. Suitable polyisocyanatesinclude diisocyanate monomers, and oligomers. Examples of polyurethanesinclude aromatic polyether polyurethanes, aliphatic polyetherpolyurethanes, aromatic polyester polyurethanes, aliphatic polyesterpolyurethanes, aromatic polycaprolactam polyurethanes, and aliphaticpolycaprolactam polyurethanes. In some other, the polyurethanes arearomatic polyether polyurethanes, aliphatic polyether polyurethanes,aromatic polyester polyurethanes, and aliphatic polyester polyurethanes.Representative commercially available examples of polyurethanes includeSancure® 2710 and/or Avalure® UR445 (which are equivalent copolymers ofpolypropylene glycol, isophorone diisocyanate, and2,2-dimethylolpropionic acid, having the International NomenclatureCosmetic Ingredient name “PPG-17/PPG-34/IPDI/DMPA Copolymer”), Sancure®878, Sancure® 815, Sancure® 1301, Sancure® 2715, Sancure® 2026, Sancure®1818, Sancure® 853, Sancure® 830, Sancure® 825, Sancure® 776, Sancure®850, Sancure® 12140, Sancure® 12619, Sancure® 835, Sancure® 843,Sancure® 898, Sancure® 899, Sancure® 1511, Sancure® 1514, Sancure®1517°, Sancure® 1591, Sancure® 2255, Sancure® 2260, Sancure® 2310,Sancure® 2725, and Sancure® 2016 (all commercially available fromLubrizol Inc.).

Other examples of commercially-available polyurethanes can includeNeoPac R-9000, R-9699, and R-9030 (available from Zeneca Resins, Ohio),Printrite® DP376 and Sancure® AU4010 (available from Lubrizol AdvancedMaterials, Inc., Ohio), and Hybridur® 570 (available from Air Productsand Chemicals Inc., Pennsylvania).

In some example, the polymeric network is created by usingcross-linkable polyglycidyl or polyoxirane resins. Cross-link reactioncan take place either with themselves (through catalytichomopolymerisation of oxirane function group) or with the help of a widerange of co-reactants including polyfunctional amines, acids, acidanhydrides, phenols, alcohols, and thiols. Both polyglycidyl resin andco-reactants are compatible with the chemicals that form a polymericnetwork before curing in liquid state. The term “compatible” refers hereto the fact that there is no significant phase separation after mixingin the room temperature.

In some examples, the first and/or the second polymeric networkcomprises epoxy-functional additives. Epoxy-functional additives caninclude alkyl and aromatic epoxy resins or epoxy-functional resins, suchas for example, epoxy novolac resin(s) and other epoxy resinderivatives. Epoxy-functional molecules can include at least one, or twoor more pendant epoxy moieties. The molecules can be aliphatic oraromatic, linear, branched, cyclic or acyclic. If cyclic structures arepresent, they may be linked to other cyclic structures by single bonds,linking moieties, bridge structures, pyro moieties, and the like.Examples of suitable epoxy functional resins are commercially availableand include, without limitation, Ancarez® AR555 (commercially availablefrom Air Products), Ancarez® AR550, Epi-rez® 3510W60, Epi-rez® 3515W6,or Epi-rez® 3522W60 (commercially available from Hexion).

In some other examples, the polymeric network includes epoxy resin.Examples of suitable aqueous dispersions of epoxy resin includeWaterpoxy® 1422 (commercially available from Cognis) or Ancarez® AR5551422 (commercially available from Air Products). The polymeric networkcan comprise epoxy resin hardeners. The examples of epoxy resinhardeners that can be used herein include liquid aliphatic orcycloaliphatic amine hardeners of various molecular weights, in 100%solids or in emulsion or water and solvent solution forms. Amine adductswith alcohols and phenols or emulsifiers can also be envisioned.Examples of suitable commercially available hardeners includeAnquawhite® 100 (from Air Products) and EN-CURE® 8290-Y-60 (fromHexion). The polymeric network can include water-based polyamine asepoxy resin hardeners. Such epoxy resin hardeners can be, for examples,water-based polyfunctional amines, acids, acid anhydrides, phenols,alcohols and/or thiols. Other examples of commercially availablepolymeric networks that can be used herein includes the ingredientsAraldite® PZ 3921 and/or Aradur® 3985 available from Huntsman.

In some examples, the image-receiving layer includes a first and/orsecond polymeric network that is a hybrid network created by usingself-cross linked polyurethane polymers and by using cross-linkablepolyglycidyl or polyoxirane resins. In some other examples, theimage-receiving layer comprises a polymeric network that is created byusing vinyl-urethane hybrid copolymers or acrylic-urethane hybridpolymers and water-based epoxy resins and water-based polyamines. In afurther example, the first and/or second crosslinked polymeric networkcan include a styrene maleic anhydride (SMA). In one example, the SMAcan include NovaCote 2000® (Georgia-Pacific Chemicals LLC, Georgia). Inanother example, the styrene maleic anhydride can be combined with anamine terminated polyethylene oxide (PEO); amine terminatedpolypropylene oxide (PPO), copolymer thereof, or a combination thereof.In one example, combining a styrene maleic anhydride with an amineterminated PEO and/or PPO can strengthen the polymeric network bycrosslinking the acid carboxylate functionalities of the SMA to theamine moieties on the amine terminated PEO and/or PPO. The amineterminated PEO and/or PPO, in one example, can include amine moieties atone or both ends of the PEO and/or PPO chain, and/or as branched sidechains on the PEO and/or PPO. In one example, utilizing an amineterminated PEO and/or PPO in combination with a SMA can allow for theuser to retain the glossy features of the SMA while eliminating thebrittle nature of SMA. Exemplary commercially available amine terminatedPEO and/or PPO compounds can include Jeffamine® XTJ-500, Jeffamine®XTJ-502, and Jeffamine® XTJ D-2000 (all available from HuntsmanInternational LLC, Texas). In some examples, a weight ratio of SMA tothe amine terminated PEO and/or PPO can range from about 100:1 to about2.5:1. In another, a weight ratio of the SMA to the amine terminated PEOand/or PPO can range from about 90:1 to about 10:1. In yet anotherexample, a weight ratio of the SMA to the amine terminated PEO and/orPPO can range from about 75:1 to about 25:1.

In some examples, the image-receiving layer might further comprisefiller particles. Such filler includes inorganic compounds, organiccompounds, compounds with flame retardancy nature, and flame-retardantagents. The filler particles can be the same or different as the oneused in the primary coating composition as described previously.

In some examples, the filler compounds have an average particle size inthe range of about 0.05 to about 25 micrometers (μm, 10⁻⁶ m). In someother examples, the inorganic compounds have an average particle size inthe range of about 0.1 to about 10 micrometers (μm). The amount offiller compound, in the image-receiving layer, can be within the rangeof about 5 to about 70 wt % or within the range of about 10 to about 60wt % or within the range of about 15 to about 50 wt % by total weight ofthe image-receiving layer. Examples of the fillers include but notlimited to, calcium carbonate, zeolite, silica, talc, alumina, aluminumtrihydrate (ATH), calcium silicate, kaolin, calcined clay, andcombination or mixtures of any of these. Examples of commercialavailable compound, also includes, but are not limited to, groundcalcium carbonate such as Hydrocarb® 60 available from Omya, Inc.;precipitated calcium carbonate such as Opacarb® 40 or Opacarb® 000available from Specialty Minerals Inc. (SMI); clay such as Miragloss®available from Engelhard Corporation; synthetic clay such as hydroussodium lithium magnesium silicate, such as, for example, Laponite®available from Southern Clay Products Inc., and titanium dioxide (TiO₂)available from, for example, Sigma-Aldrich Co. Examples of fillersinclude, but are not limited to, compound, either existing in adispersed slurry or in a solid powder, of polystyrene and itscopolymers, polymethyacrylates and their copolymers, polyacrylates andtheir copolymers, polyolefins and their copolymers, such as polyethyleneand polypropylene, a combination of two or more of the polymers. Thefiller compound may be chosen from silica gel (e.g., Silojet® 703Cavailable from Grace Co.), modified (e.g., surface modified, chemicallymodified, etc.) calcium carbonate (e.g., Omyajet® B6606, C3301, and5010, all of which are available from Omya, Inc.), precipitated calciumcarbonate (e.g., Jetcoat® 30 available from Specialty Minerals, Inc.),and combinations thereof.

In addition to the above-described components, the image-receiving layermight contain other components or additives. The additives include, butare not limited to, one or more of rheology modifiers, thickeningagents, cross-linking agents, surfactants, defoamers, opticalbrighteners, dyes, pH controlling agents or wetting agents, anddispersing agents, for example. The total amount of additives, in thecomposition for forming the treatment composition, can be from about 0.1wt % to about 10 wt % or from about 0.2 wt % to about 5 wt %, by totaldry weight of the treatment composition.

Method for Forming a Fabric Print Medium

The fabric print medium is prepared by using a surface treatmentcomposition herein named a coating layer or coating composition. In someexamples, the method for forming the fabric print medium encompasses:providing a fabric base substrate (110) with a first and a second side(i.e. with an image side (101) and a backside (102)); applying a primarycoating composition (130), including a polymeric binder and fillerparticles, on one side of the fabric base substrate; applying a barrierlayer (120) comprising a water-repellent agent and a physical gellingcompound to the other side of the fabric base substrate, opposite to theprimary coating composition (130); and applying an image-receivingcoating composition (140) including a first crosslinked polymericnetwork and a second crosslinked polymeric network, over the primarycoating composition (140).

The method encompasses applying primary coating composition (130) on theimage side (101) of the fabric base substrate (110), then applyingbarrier layer (120) on the backside (102) of the fabric base substrate(110) and finally applying the image-receiving coating composition (140)over the primary coating composition (140) on the image side (101) ofthe media. The primary coating composition is applied directly over thefabric substrate and followed by the application of the barrier layer onthe opposite side of said primary coating composition. To avoid anypenetration of the primary coating composition in the fabric basesubstrate, an organic thickener can be included in the primary coatingformulation to obtain a primary coating solution with a high viscosity.In some examples, the viscosity of primary coating solution ranges from4,000 cps to 30,000 cps under the spindle speed of 100 rpm using aBrookfield viscometer, when measured at room temperature. In someexamples, the viscosity of primary coating solution ranges from about4,000 cps to about 8,000 cps, e.g., the viscosity of the composition ismeasured at room temperature at a speed of 100 rpm by a Brookfieldviscometer.

In some examples, a fabric print medium with one printing side ispresented. The primary coating compositions can independently include apolymeric binder and filler particles. The secondary coating layers canbe applied to the primary coating composition on both the first side andthe second side at an independent thickness from 1 μm to 50 μm with anindependent dry coat weight ranging from 0.5 gsm to 50 gsm. Thesecondary coating layers can independently include a first crosslinkedpolymeric network and a second crosslinked polymeric network. Theprimary coating compositions can be two or more times thicker than theirrespective immediately adjacent secondary coating layer. The term“independently” is used in this example to indicate that though bothsides have the same general parameters, the respective layers on eachside does not need to be identical.

The application of the barrier layer, the primary coating composition(primary layer) and of the image-receiving coating composition(secondary coating layer) can include a floating knife process, a knifeon roll mechanism process, or a transfer coating process. The floatingknife process can include stretching the fabric to form an even uniformsurface. The floating knife process can further include transporting thefabric under a stationary knife blade. In some examples, the step ofapplying the primary and secondary coating layer can include applying afoam coating. The foam coating can be applied using a knife-on-the rollmechanism. The knife-on-the roll mechanism can be followed by passingthe fabric through calendaring pressure nips. The calendaring can bedone either in room temperature or at an elevated temperature and/orpressure. The elevated temperature can range from 40° C. to 100° C. Theelevated pressure can range from about 100 psi to about 5,000 psi. Insome other examples, the coating process can include transferring thecoating composition. When the coating composition is transferred, thecoating can be spread onto a release substrate to form a film. The filmcan then be laminated onto the fabric.

Coating compositions can be dried using box hot air dryer. The dryer canbe a single unit or could be in a serial of 3 to 8 units so that atemperature profile can be created with initial lower temperature (toremove excessive water) and mild temperature in end units (to ensurecompletely drying with a final moisture level of less than 1-5% forexample). The peak dryer temperature can be programmed into a profilewith lower to moderate temperature at begging of the drying when wetmoisture is high and then go through peak temperature range to ensurethe coating is dried and cross-linked if required. At the end ofprofile, the web temperature is reduced to lower temperature when webbecoming dry. The dryer temperature is controlled to a temperature ofless than about 200° C. peak temperature to avoid yelling textile, andthe fabric web temperature is controlled in the range of about 90 toabout 180° C. In some examples, the operation speed of thecoating/drying line is 20 meters per minute for primary and top imagereceiving coatings and 30-50 meters per minute for barrier coatingcomposition.

In some examples, the method can further include applying pressure usingpressure nips equipped on the coater meaning calendaring the web withthe same speed as coating, or off-line calendar, under single ormultiple calendaring nips to the fabric media after applying the primaryand top coating layer, or only after applying the top coating layer,with the same or different calendaring speed.

Printing Method

Once the coating composition is applied to the fabric base substrate andappropriately dried, ink compositions can be applied by any processesonto the fabric print medium. In some examples, the ink composition isapplied to the fabric print medium via inkjet printing techniques. Theprinting method (300) encompasses obtaining a fabric print mediumcontaining a fabric base substrate; a barrier layer comprising awater-repellent agent and a physical gelling compound applied to, atleast, one side of the fabric base substrate; a primary coatingcomposition including a polymeric binder and filler particles, appliedon the fabric base substrate, on the opposite side of the barrier layer;and an image-receiving coating composition including a first and asecond crosslinked polymeric network applied over the primary coatingcomposition (310); and, then, applying an ink composition onto saidfabric print medium to form a printed image (320). Said printed imagewill have, for instance, enhanced image quality and image permanence. Insome examples, when needed, the printed image can be dried using anydrying device attached to a printer such as, for instance, an IR heater.

In some examples, the ink composition is an inkjet ink composition thatcontains one or more colorants that impart the desired color to theprinted message and a liquid vehicle. As used herein, “colorant”includes dyes, pigments, and/or other particulates that may be suspendedor dissolved in an ink vehicle. The colorant can be present in the inkcomposition in an amount required to produce the desired contrast andreadability. In some examples, the ink compositions include pigments ascolorants. Pigments that can be used include self-dispersed pigments andnon-self-dispersed pigments. Any pigment can be used; suitable pigmentsinclude black pigments, white pigments, cyan pigments, magenta pigments,yellow pigments, or the like. Pigments can be organic or inorganicparticles as well known in the art. As used herein, “liquid vehicle” isdefined to include any liquid composition that is used to carrycolorants, including pigments, to a substrate. A wide variety of liquidvehicle components may be used and include, as examples, water or anykind of solvents.

In some other examples, the ink composition, applied to the fabric printmedium, is an ink composition containing latex components. Latexcomponents are, for examples, polymeric latex particulates. The inkcomposition may contain polymeric latex particulates in an amountrepresenting from about 0.5 wt % to about 15 wt % based on the totalweight of the ink composition. The polymeric latex refers herein to astable dispersion of polymeric micro-particles dispersed in the aqueousvehicle of the ink. The polymeric latex can be natural latex orsynthetic latex. Synthetic latexes are usually produced by emulsionpolymerization using a variety of initiators, surfactants and monomers.In various examples, the polymeric latex can be cationic, anionic,nonionic, or amphoteric polymeric latex. Monomers that are often used tomake synthetic latexes include ethyl acrylate; ethyl methacrylate;benzyl acrylate; benzyl methacrylate; propyl acrylate; methylmethacrylate, propyl methacrylate; iso-propyl acrylate; iso-propylmethacrylate; butyl acrylate; butyl methacrylate; hexyl acrylate; hexylmethacrylate; octadecyl methacrylate; octadecyl acrylate; laurylmethacrylate; lauryl acrylate; hydroxyethyl acrylate; hydroxyethylmethacrylate; hydroxyhexyl acrylate; hydroxyhexyl methacrylate;hydroxyoctadecyl acrylate; hydroxyoctadecyl methacrylate; hydroxylaurylmethacrylate; hydroxylauryl acrylate; phenethyl acrylate; phenethylmethacrylate; 6-phenylhexyl acrylate; 6-phenylhexyl methacrylate;phenyllauryl acrylate; phenyllauryl methacrylate; 3-nitrophenyl-6-hexylmethacrylate; 3-nitrophenyl-18-octadecyl acrylate; ethyleneglycoldicyclopentyl ether acrylate; vinyl ethyl ketone; vinyl propyl ketone;vinyl hexyl ketone; vinyl octyl ketone; vinyl butyl ketone; cyclohexylacrylate; methoxysilane; acryloxypropyhiethyldimethoxysilane;trifluoromethyl styrene; trifluoromethyl acrylate; trifluoromethylmethacrylate; tetrafluoropropyl acrylate; tetrafluoropropylmethacrylate; heptafluorobutyl methacrylate; butyl acrylate; iso-butylmethacrylate; 2-ethylhexyl acrylate; 2-ethylhexyl methacrylate; isooctylacrylate; and iso-octyl methacrylate.

In some examples, the latexes are prepared by latex emulsionpolymerization and have an average molecular weight ranging from about10,000 Mw to about 5,000,000 Mw. The polymeric latex can be selectedfrom the group consisting of acrylic polymers or copolymers, vinylacetate polymers or copolymers, polyester polymers or copolymers,vinylidene chloride polymers or copolymers, butadiene polymers orcopolymers, polystyrene polymers or copolymers, styrene-butadienepolymers or copolymers and acrylonitrile-butadiene polymers orcopolymers. The latex components are on the form of a polymeric latexliquid suspension. Such polymeric latex liquid suspension can contain aliquid (such as water and/or other liquids) and polymeric latexparticulates having a size ranging from about 20 nm to about 500 nm orranging from about 100 nm to about 300 nm.

EXAMPLES

The raw materials and chemical components used in the illustratingsamples are listed in Table 1.

TABLE 1 Ingredients Nature of the ingredients Supplier Araldite ® PZCross-linked polymeric network Hundtsman Inc. 3901 Aradur ® 3985Cross-linked polymeric network Hundtsman Inc. SpaceRite ® S3 Aluminumtri-hydroxide (filler J.M. Huber & flame-retardant agent) Corp.Byk-Dynwet ® 800 silicone-free wetting agent BYK Inc. Tegowet ® 510Surfactant Evonik Industries Sancure ®2026 Polyurethane polymer LubrizolInc. Sancure ® AU4010 Self-Crosslinking aliphatic Lubrizol Inc.polyurethane-acrylic network Edolan ® AB Polymeric binder TanatexChemicals Foamaster ® De-former BASF Co. MO2185 Tylose ®H 100000physical gelling compound Shin-Etsu Ltd YP2

Example 1—Preparation of Printable Medium Samples

The illustrating sample 1 is fabric print medium in accordance with theprinciples described herein. Samples 2, 3 and 4 are comparativeexamples. Detailed structures of these samples are shown in Table 2.Each samples have a support base structure (110) which is a 100% wovenpolyester fabric having a weight of 112 gsm and thickness of 175micrometers (μm), a barrier layer (120), a primary coating composition(130) and an image-receiving coating layer (140). The differentformulations of the barrier layer (120), primary coating composition(130) and image-receiving coating layer (140) are illustrated in thetables 3 and 4.

TABLE 2 Primary coating Image-receiving composition PC coating layerSamples Barrier layer (120) (130) IRC (140) Sample 1 B1 PC formulationIRC formulation applied on top of the applied on top of applied on topof fabric base, opposite fabric substrate, PC, 5 gsm side of PC/IRC 2 20gsm gsm Sample 2 B2 PC formulation IRC formulation Compar- applied ontop of the applied on top of applied on top of ative fabric base, sameside B2, 20 gsm PC, 5 gsm of PC/IRC 2 gsm Sample 3 B3 PC formulation IRCformulation Compar- applied on top of the applied on top of applied ontop of ative fabric base, opposite fabric substrate, PC, 5 gsm side ofPC/IRC 2 20 gsm gsm Sample 4 None PC formulation IRC formulation Compar-applied on top of applied on top of ative fabric base, 20 PC, 5 gsm gsm

A 2.4 m width production knife on air fabric coater are used to producethe fabric print medium samples 1 to 4. During processing, the coatingcompositions (fluids) are applied directly to the textile fabric andspread in a uniform manner by means of a fixed knife. The thickness ofthe coatings, or coat-weight, is controlled by the gap between thebottom of the knife and the top of the fabric. A 2 mm flat tip blade(knife) is use for the barrier coating and the image-receiving coating,while the primary coating is accomplished by use a 3 mm U-type blade.The depth of blade is 1 cm. The coating speed for the barrier layer isin the range of 30 to 40 m/min while primary and image-receiving coatingare applied under a speed of 20 m/min. After the coating compositionsare applied on the fabric web, the web is gone through a 40 m long hotair dryer with multiple (8) controlled units so that a dryingtemperature profile can be set (For example, one of the setting coatingis 110° C., 120° C., 130° C., 130° C., 130° C., 130° C., 115° C. and 90°C.). A on-line pressure nip is also closed to the primary andimage-receiving coatings to further smooth-out the surface. Theformulations of the primary coating (130), i.e. PC, and the formulationsof the image-receiving coating composition (140), i.e. IRC, areillustrated in Table 4 below.

TABLE 3 Barrier layer Baygard ® Tylose ® H (120) WRS 100000 CoatingSequence B1 10 g/L 1% After primary coating, opposite side as primarycoating B2 10 g/L 1% Before primary coating, (Comparative) same side asprimary coating B3 10 g/L — After primary coating, (Comparative)opposite side as primary coating

TABLE 4 Ingredient Amount (Parts by dry weight) Primary Coating (130) -PC Edolan ® AB 40 Spacerite ® S3 100 Tegowet ® 510 1 Foamaster MO21850.5 Image-receiving coating (140) - IRC Byk-Dynwet ® 800 1 Araldite ® PZ3901 10 Aradur ® 3985 10 Sancure ® 2016 5.8 Sancure ® 4010 3.5

Example 2—Samples Performances

The same images are printed on the experimental Sample 1 and ComparisonSamples 2, 3 and 4 using a HP® DesignJet L360 Printer equipped with HP789 ink cartridge (HP Inc.). The printer is set with a heating zonetemperature at about 50° C., a cure zone temperature at about 110° C.,and an air flow at about 15%. The printed fabric mediums are evaluatedfor different performances: image quality, image durability and softfeeling. The results of these tests are expressed in the Table 5 below.

Image quality is evaluated using both numeric measurement method andvisual evaluation method. Image quality tests are conducted by measuringthe color gamut, using XYZ color patches on Macbeth® TD904 device (MicroPrecision Test Equipment, California). The image quality of the printsrelated to bleed sharpness, blur, noise/graininess, banding, mottle,patchiness, line quality, and text quality, are evaluated visually fromthe printed samples using a scale of 1-5 (with 1 being the worst and 5being the best).

The image durability test is performed by exposing the various samplesto be tested to a 45 degree coin scratching under a normal force of 800g. The test is done in a BYK Abrasion Tester (from BYK-Gardner USA,Columbus, Md.) with a linear, back-and-forth action, attempting toscratch off the image side of the samples (5 cycles). The imagedurability is evaluated visually from the printed samples using a scaleof 1-5 (with 1 being the worst and 5 being the best).

The softness is evaluated “manually”, by multiple operators (n=5) byinitial hand feeling. An average score of 1 was given when resentingstiff and serious wrinkling, and a score of 5 was given if the whenresenting soft and insignificant wrinkling.

TABLE 5 Test Results Sample Image Quality Image Durability Soft feelingExample 1 5 5 5 Example 2 (comp.) 5 2  4+ Example 3 (comp.) 3 1 5Example 4 (comp.) 3 5 2

The coating quality and the results observed during the coating processare observed and reported. Such results are shown in the table 6 below

TABLE 6 Test Results Sample Results Observed during Coating Example 1Smooth run, no significant de-watering over 0.45/1 hrs. continuousmachine running. Base coating quality score 5, and top coating qualityscore 5 Example 2 Smooth run, no significant de-watering over (comp.)0.45/1 hrs. Continuous machine running. Base coating quality score 2-3,and top coating quality score 5 Example 3 running able, slightlyde-watering over (comp.) 0.45/1 hrs. continuous machine running. Basecoating quality score 5, and top coating quality score 3 Example 4 A lotof “yogurt-like” gelling produced (comp.) during top coating after 5 minmachine running. Machine forced to stop. Base coating quality score 4.Some contamina- tion to moving rolls.

As can be seen by the test results above, the fabric print mediumaccording to the present disclosure provides several advantages over thecomparative samples in terms of image quality, image durability and“soft hands feeling” performances as well as easy of the coatingprocess. It is noted that though some comparative medium performed wellin some categories, they performed poorly in others. In accordance withexamples of the present disclosure, over these tests, performance iscollectively better when using the fabric print medium described herein.

The invention claimed is:
 1. A fabric print medium comprising: a. afabric base substrate with a first and a second side; b. a barrierlayer, comprising a water-repellent agent and a physical gellingcompound, applied to one side of the fabric base substrate; c. a primarycoating composition, including a polymeric binder and filler particles,applied on the fabric base substrate, on the opposite side of thebarrier layer; d. and an image-receiving coating composition, includinga first and a second crosslinked polymeric network, applied over theprimary coating composition.
 2. The fabric print medium of claim 1wherein, in the barrier layer, the water-repellent agent is ahydrophobic compound with long paraffin chains having the formula CnHn+2where n is equal or superior to
 6. 3. The fabric print medium of claim 1wherein, in the barrier layer, the water-repellent agent is selectedfrom the group consisting of polyvinylidene chloride emulsion,polyolefin emulsion, poly(ethyl-terephthalate) emulsion, aqueous waxdispersion, perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid(PFOA) and emulsion of a hydrogen siloxane.
 4. The fabric print mediumof claim 1 wherein, in the barrier layer, the physical gelling compoundis a polymer having a molecular weight ranging from about 300,000 toabout 1,000,000.
 5. The fabric print medium of claim 1 wherein, in thebarrier layer, the physical gelling compound is selected from the groupconsisting of copolymers of acrylates, copolymers with acrylate basedpolyelectrolyte backbone, copolymers with polyester backbone, andcopolymers with polyurethane based copolymer backbone.
 6. The fabricprint medium of claim 1 wherein the barrier layer is applied to thefabric base substrate at a dry coat weight ranging from about 0.05 gsmper side to about 5 gsm per side.
 7. The fabric print medium of claim 1wherein the primary coating composition comprises a flow-controllingagent.
 8. The fabric print medium of claim 7 wherein, in the primarycoating composition, the flow-controlling agent is modifiedpolysaccharide compound.
 9. The fabric print medium of claim 1 whereinthe primary coating composition is applied directly over the fabricsubstrate, on the opposite side of the barrier layer, at a dry coatweight ranging from about 5 gsm to about 200 gsm.
 10. The fabric printmedium of claim 1 wherein the primary coating composition has aviscosity ranging from about 4,000 cps to about 30,000 cps when measuredat room temperature.
 11. The fabric print medium of claim 1 wherein, inthe primary coating composition, the polymeric binder is a polymer or acopolymer selected from the group consisting of acrylic polymers orcopolymers, vinyl acetate polymers or copolymers, polyester polymers orcopolymers, vinylidene chloride polymers or copolymers, butadienepolymers or copolymers, styrene-butadiene polymers or copolymers andacrylonitrile-butadiene polymers or copolymers.
 12. The fabric printmedium of claim 1 wherein, in the image-receiving coating composition,the first crosslinked polymeric network and the second crosslinkedpolymeric network are different and independently comprisespolyacrylate, polyurethane, vinyl-urethane, acrylic urethane,polyurethane-acrylic, polyether polyurethane, polyester polyurethane,polycaprolactam polyurethane, polyether polyurethane, alkyl epoxy resin,epoxy novolac resin, polyglycidyl resin, polyoxirane resin, polyamine,styrene maleic anhydride, a derivative thereof, or a combinationthereof.
 13. An image recoding medium comprising: a. a fabric basesubstrate with a first and a second side; b. a barrier layer, comprisinga hydrophobic compound with long paraffin chains and a physical gellingcompound, applied to one side of the fabric base substrate; c. a primarycoating composition including a polymeric binder, filler particles and aflow-controlling agent, applied on the fabric base substrate, on theopposite side of the barrier layer; d. and an image-receiving coatingcomposition applied over the primary coating composition.
 14. A methodfor forming a fabric print medium comprising: a. providing a fabric basesubstrate with a first and a second side; b. applying a primary coatingcomposition, including a polymeric binder and filler particles, on oneside of the fabric base substrate; c. applying a barrier layer on theother side of the fabric base substrate, opposite to the primary coatingcomposition; d. and applying an image-receiving coating compositionincluding a first and a second crosslinked polymeric network, over theprimary coating composition.
 15. A printing method comprising: a.obtaining a fabric print medium comprising a fabric base substrate; abarrier layer comprising a water-repellent agent and a physical gellingcompound applied to, at least, one side of the fabric base substrate; aprimary coating composition including a polymeric binder and fillerparticles, applied on the fabric base substrate, on the opposite side ofthe barrier layer; and an image-receiving coating composition includinga first and a second crosslinked polymeric network applied over theprimary coating composition; b. and applying an ink composition ontosaid fabric print medium to form a printed image.